CN103304376A - Clean production process of alkyne diol serial products - Google Patents
Clean production process of alkyne diol serial products Download PDFInfo
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- CN103304376A CN103304376A CN2013102473429A CN201310247342A CN103304376A CN 103304376 A CN103304376 A CN 103304376A CN 2013102473429 A CN2013102473429 A CN 2013102473429A CN 201310247342 A CN201310247342 A CN 201310247342A CN 103304376 A CN103304376 A CN 103304376A
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- alkyne diol
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Abstract
The invention relates to a clean production process of alkyne diol serial products, and aims to provide a clean production process of the alkyne diol serial products mild in reaction condition and low in production cost. The clean production process of the alkyne diol serial products comprises the following steps: adding an organic solvent into a reaction kettle, standing, and then, adding alkali metal hydroxide; respectively adding acetylene and ketone by a pump into the reaction kettle for a reaction, and controlling the feeding speed, wherein in the feeding process, the pressure in the reaction kettle is not greater than 0.08MPa; after reaction, cooling to below 50 DEG C, and adding water to stir; and dropping an acid to adjust pH to 3-4, washing by water, standing and layering, and decompressing and distilling to recover n-heptane to obtain the product. According to the process provided by the invention, the use level of catalyst is fewer, so that the product belongs to bulk chemical product and the cost is low. The process temperature is not higher than 80 DEG C, the pressure is not greater than 0.08MPa, and the condition is mild. The yield of alkyne diol synthesized is greater than 85%. The solvent is decompressed, distilled, recovered and recycled, and no discharge waste exists.
Description
Technical field
The present invention relates to a kind of production technique of alkyne diol series product, be specifically related to a kind of process for cleanly preparing of alkyne diol series product.
Background technology
Alkyne diol has the nonionic surface active agent of special construction as a class, all have widely purposes at numerous areas, such as agricultural chemicals, pharmaceutical-chemical intermediate, metal treatment, synthetic materials and daily-use chemical industry etc.
The synthetic of alkyne diol starts from 1900, passed through the development in century more than.The producer that produces alkynol on the our times is no more than ten, and wherein maximum is the gas chemical industry of the U.S., secondly is the BASF of Germany, and grind in Japanese river, and except Eastern Europe also had a manufacturer production, all the other had been exactly three to four producers of China's Mainland.
In the prior art, the synthetic method of alkynol roughly comprises following several:
1, the pressurization of the low temperature take liquefied ammonia as solvent system synthetic method;
2, with grignard reagent or the alkyl lithium reagents atmospheric synthesizing method as catalyzer;
3, the process for catalytic synthesis take basic metal and oxyhydroxide thereof as catalyzer;
4, potassium alcoholate process for catalytic synthesis;
5, the novel method for synthesizing take anionite-exchange resin as carrier.
These synthetic methods have needs hyperbaric environment, the catalyzer that some needs are special, and not only production cost is high, but also can produce a large amount of waste water, to environment.
Summary of the invention
Main purpose of the present invention provides the process for cleanly preparing of the alkyne diol series product that a kind of reaction conditions is gentle, production cost is low.
For achieving the above object, the technical solution used in the present invention is: a kind of process for cleanly preparing of alkyne diol series product comprises step:
A. organic solvent is added reactor, leave standstill, add again alkali metal hydroxide;
B. acetylene and ketone are added the reactor reaction with pump respectively, by the control feed rate so that in the reinforced process reacting kettle inner pressure be not higher than 0.08MPa;
C. after reaction finishes, be cooled to and be lower than 50 ℃, add entry and stir;
D. drip acid for adjusting pH to 3～4, washing, standing demix, organic solvent is reclaimed in underpressure distillation, namely gets product.
Basic metal is all metallic elements in the periodic table of elements IA family element, and alkali metal hydroxide is the oxyhydroxide of alkali metal, such as sodium hydroxide, potassium hydroxide, lithium hydroxide etc.Increased pressure in the reaction process reduces the feed rate of acetylene, otherwise, then increase the feed rate of acetylene.
Further, described acetylene flow range is 2.5～15m
3/ h.When that is to say in the conditioned reaction still pressure, the flow of acetylene is at 2.5～15m
3Change in the scope of/h.
Further, described organic solvent is the liquid aliphatic hydrocarbon.Aliphatic hydrocarbon namely is the organic compound or derivatives thereof that is made of hydrocarbon chain, and the liquid aliphatic hydrocarbon is the organic compound that liquid hydrocarbon chain consists of.
Further preferably, described organic solvent is normal heptane.Normal heptane belongs to large Chemicals, is easy to get, and its moderate boiling point, stable in properties is difficult for side reaction occurs in reaction, and also is easier to and product separation when distillating recovering solvent.
Further preferably, the described alkali metal hydroxide potassium hydroxide that is sheet.The form of potassium hydroxide is generally powder or sheet, herein the potassium hydroxide of sheet preferably.And potassium hydroxide can also be produced potash fertilizer in Recycling of waste liquid.
Further preferably, the mol ratio of described alkali metal hydroxide and ketone is: 1:0.5～1.5.Alkali metal hydroxide does not reach required catalytic effect as catalyzer at least if consumption is crossed, if consumption is crossed the more salt of generation when separating in the later stage at most.
Further preferably, the contained amount of carbon atom of described ketone is 3～8.Experimental results show that amount of carbon atom is 3～8 and adopts preparation method of the present invention can obtain higher yield.
Further preferably, described ketone is methyl iso-butyl ketone (MIBK) or methyl isoamyl ketone.
Further, described acid is hydrochloric acid or acetic acid.These two kinds of acid are more stable, store easily, and are less to operator's harm, can certainly be other acid, such as sulfuric acid, formic acid etc.
Further, pass into nitrogen or inert gas replacement in the described reactor before adding acetylene and the ketone.Rare gas element is helium, neon, argon, krypton, xenon, radon gas body, that is to say before adding reactant and first the air in the reactor is replaced with nitrogen or other rare gas element, so that the atmosphere of reaction is oxygen-free environment, this is in order to reduce the generation of side reaction.
Each parameter is the optimal processing parameter that participates in reaction in the technique scheme, but the variation that those skilled in the art can instruction according to the present invention be equal to.For example: because the parameter that the error of industrial production itself causes changes and technical scheme of the present invention is equal to, composite other assisted and be equal to agent and technical scheme of the present invention on prescription of the present invention basis.
The present invention is the normal temperature and pressure catalysis synthetic method take normal heptane as solvent, has following characteristics:
1, the catalyst levels that uses is few, and is common large Chemicals, is easy to get, and cost is low.
2, technological temperature is not higher than 80 ℃, and pressure is not higher than 0.08MPa, and employed pressurized vessel is normal pressure.
3, synthetic alkyne diol productive rate all is higher than 85%;
4, solvent is normal heptane, and reaction finishes by the step-down Distillation recovery, and is reusable, without the discharging waste.
And alkali metal hydroxide transfers alkali hydroxide soln to after reaction, can reclaim by alkali recovery boiler, reuse after making with extra care, wherein potassium hydroxide can also generate salt of wormwood or saleratus with carbon dioxide reaction, use as potash fertilizer, without exhaust emission.
Embodiment
For those skilled in the art are known and clear and definite technical scheme of the present invention more, the spy provides following preferred embodiment, but technological thought of the present invention is not limited to following examples.
Embodiment one
After with pump the 2535kg normal heptane being delivered to header tank metering, it is added to volume is in 5000 liters the reactor; With pump the 450kg methyl iso-butyl ketone (MIBK) is delivered to header tank.Normal heptane adds 300kg sodium hydroxide after feeding intake and finishing to leave standstill 30 minutes minutes water, feeds intake to build the lid that feeds intake after finishing, and screws bolt.
With nitrogen replacement 15 minutes, close blow-off valve with nitrogen leak test pressure testing (pressure is less than 0.04MP), slowly pass into 62kg acetylene after pressure testing finishes and begin reaction: the acetylene flow control is at 2.5～15m
3/ h, step of reaction is controlled the still internal pressure less than 0.08MPa by regulating the acetylene flow.
Reaction slightly cools to 48 ℃ after finishing, and beginning slowly adds water 800kg, adds to stir 30 minutes after water finishes.Material is pressed among the 5000L and still in.After binder finishes, left standstill 30 minutes, slowly arrange alkali lye to lye vat, be pumped to again the alkali lye storage tank.After row's alkali lye finishes, stir and leave standstill again the alkali lye emptying that will remain in the material.After slowly dripping salt acid for adjusting pH to 4 again, stirred 30 minutes, left standstill 15 minutes, with pump mass transport to washing kettle is washed behind the filtering solid salt.
Water-washing step is: will in and still in material divide equally to the washing kettle of two 2000L, every still adds water 200kg/ time, washes twice, each washing churning time 30 minutes, leave standstill again draining after 30 minutes, material is left standstill 2 little layereds, the lower layer of water of draining with pump delivery to the oil phase groove.
At last with material in the oil phase groove with pump delivery to still kettle, underpressure distillation stops distillation during to solvent-free outflows, namely gets product 2,4,7,9-tetramethyl--5-decine-4, the 7-glycol, the calculating productive rate is 92%.
Embodiment two
After with pump the 2636kg normal heptane being delivered to header tank metering, it is added to volume is in 5000 liters the reactor; With pump the 450kg methyl iso-butyl ketone (MIBK) is delivered to header tank.Normal heptane adds 350kg potassium hydroxide after feeding intake and finishing to leave standstill 30 minutes minutes water, feeds intake to build the lid that feeds intake after finishing, and screws bolt.
With nitrogen replacement 20 minutes, close blow-off valve with nitrogen leak test pressure testing (pressure is less than 0.04MP), slowly pass into 63kg acetylene after pressure testing finishes and begin reaction: the acetylene flow control is at 2.5～15m
3/ h, step of reaction is controlled the still internal pressure less than 0.08MPa by regulating the acetylene flow.
Reaction slightly cools to 48 ℃ after finishing, and beginning slowly adds water 800kg, adds to stir 30 minutes after water finishes.Material is pressed among the 5000L and still in.After binder finishes, left standstill 30 minutes, slowly arrange alkali lye to lye vat, be pumped to again the alkali lye storage tank and be used for producing potash fertilizer with the carbon dioxide gas precursor reactant.After row's alkali lye finishes, stir and leave standstill again the alkali lye emptying that will remain in the material.After slowly dripping salt acid for adjusting pH to 3～4 again, stirred 30 minutes, left standstill 15 minutes, with pump mass transport to washing kettle is washed behind the filtering solid salt.
Water-washing step is: will in and still in material divide equally to the washing kettle of two 2000L, every still adds water 200kg/ time, washes twice, each washing churning time 30 minutes, leave standstill again draining after 30 minutes, material is left standstill 2 little layereds, the lower layer of water of draining with pump delivery to the oil phase groove.
At last with material in the oil phase groove with pump delivery to still kettle, underpressure distillation stops distillation during to solvent-free outflows, namely gets product 2,4,7,9-tetramethyl--5-decine-4, the 7-glycol, the calculating productive rate is 93%.
Embodiment three
After with pump the 2695kg normal hexane being delivered to header tank metering, it is added to volume is in 5000 liters the reactor; With pump 550kg2-methyl-2 pentanone is delivered to header tank.Normal heptane adds 300kg potassium hydroxide after feeding intake and finishing to leave standstill 30 minutes minutes water, feeds intake to build the lid that feeds intake after finishing, and screws bolt.
With nitrogen replacement 20 minutes, close blow-off valve with nitrogen leak test pressure testing (pressure is less than 0.04MP), slowly pass into 65kg acetylene after pressure testing finishes and begin reaction: the acetylene flow control is at 2.5～15m
3/ h, step of reaction is controlled the still internal pressure less than 0.08MPa by regulating the acetylene flow.
Reaction slightly cools to 45 ℃ after finishing, and beginning slowly adds water 1000kg, adds to stir 30 minutes after water finishes.Material is pressed among the 5000L and still in.After binder finishes, left standstill 30 minutes, slowly arrange alkali lye to lye vat, be pumped to again the alkali lye storage tank.After row's alkali lye finishes, stir and leave standstill again the alkali lye emptying that will remain in the material.After slowly dripping salt acid for adjusting pH to 3～4 again, stirred 30 minutes, left standstill 15 minutes, with pump mass transport to washing kettle is washed behind the filtering solid salt.
Water-washing step is: will in and still in material divide equally to the washing kettle of two 2000L, every still adds water 200kg/ time, washes twice, each washing churning time 30 minutes, leave standstill again draining after 30 minutes, material is left standstill 2 little layereds, the lower layer of water of draining with pump delivery to the oil phase groove.
At last with material in the oil phase groove with pump delivery to still kettle, underpressure distillation stops distillation during to solvent-free outflows, namely gets product 2,5,8,11-tetramethyl--6-dodecyne-5, the 8-glycol, the calculating productive rate is 90%.
Claims (10)
1. the process for cleanly preparing of alkyne diol series product is characterized in that: comprise step:
A. organic solvent is added reactor, leave standstill, add again alkali metal hydroxide;
B. acetylene and ketone are added the reactor reaction with pump respectively, by the control feed rate so that in the reinforced process reacting kettle inner pressure be not higher than 0.08MPa;
C. after reaction finishes, be cooled to and be lower than 50 ℃, add entry and stir;
D. drip acid for adjusting pH to 3～4, washing, standing demix, organic solvent is reclaimed in underpressure distillation, namely gets product.
2. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: described acetylene flow range is 2.5～15m
3/ h.
3. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: described alkali metal hydroxide is the potassium hydroxide of sheet.
4. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: the mol ratio of described alkali metal hydroxide and ketone is: 1:0.5～1.5.
5. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: described organic solvent is aliphatic hydrocarbon or aromatic hydrocarbons.
6. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: described organic solvent is normal heptane.
7. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: the contained amount of carbon atom of described ketone is 3～8.
8. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: described ketone is methyl iso-butyl ketone (MIBK) or methyl isoamyl ketone.
9. the process for cleanly preparing of alkyne diol series product according to claim 1, it is characterized in that: described acid is hydrochloric acid or acetic acid.
10. the process for cleanly preparing of alkyne diol series product according to claim 1 is characterized in that: pass into nitrogen or inert gas replacement before adding acetylene and ketone in the described reactor.
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| CN2013102473429A CN103304376A (en) | 2013-06-20 | 2013-06-20 | Clean production process of alkyne diol serial products |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963960A (en) * | 2017-12-18 | 2018-04-27 | 王建华 | A kind of new process for synthesizing acetylenic glycols |
| CN113717031A (en) * | 2021-09-27 | 2021-11-30 | 四川众邦制药有限公司 | Method for coproducing tetramethyldodecynediol and dimethylheptynediol |
| CN114835557A (en) * | 2022-05-13 | 2022-08-02 | 重庆康普化学工业股份有限公司 | Method for co-producing TMDD (TMDD) by using MIBK (methyl isobutyl ketone) as solvent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112544A (en) * | 1994-11-17 | 1995-11-29 | 泸州宏达有机化工厂 | Benzene-hydrosolvent method for processing hexyndiol |
| CN1224411A (en) * | 1996-09-03 | 1999-07-28 | 巴斯福股份公司 | Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools |
| CN1312784A (en) * | 1998-08-17 | 2001-09-12 | 巴斯福股份公司 | Process for preparing alkyndialcohol |
| CN102964216A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工有限公司 | Decyne glycol synthesizing technology |
-
2013
- 2013-06-20 CN CN2013102473429A patent/CN103304376A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112544A (en) * | 1994-11-17 | 1995-11-29 | 泸州宏达有机化工厂 | Benzene-hydrosolvent method for processing hexyndiol |
| CN1224411A (en) * | 1996-09-03 | 1999-07-28 | 巴斯福股份公司 | Process for preparing alkyne diols or mixtures of alkyne diols with alkyne monools |
| CN1312784A (en) * | 1998-08-17 | 2001-09-12 | 巴斯福股份公司 | Process for preparing alkyndialcohol |
| CN102964216A (en) * | 2012-12-06 | 2013-03-13 | 盘锦科隆精细化工有限公司 | Decyne glycol synthesizing technology |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107963960A (en) * | 2017-12-18 | 2018-04-27 | 王建华 | A kind of new process for synthesizing acetylenic glycols |
| CN113717031A (en) * | 2021-09-27 | 2021-11-30 | 四川众邦制药有限公司 | Method for coproducing tetramethyldodecynediol and dimethylheptynediol |
| CN113717031B (en) * | 2021-09-27 | 2024-04-12 | 四川众邦新材料股份有限公司 | Method for co-production of tetramethyl-dodecynediol and dimethyl heptynol |
| CN114835557A (en) * | 2022-05-13 | 2022-08-02 | 重庆康普化学工业股份有限公司 | Method for co-producing TMDD (TMDD) by using MIBK (methyl isobutyl ketone) as solvent |
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Application publication date: 20130918 |